Two-Photon Light Trigger siRNA Transfection of Cancer Cells Using Non-Toxic Porous Silicon Nanoparticles.

The concept of using two-photon excitation in the NIR for the spatiotemporal control of biological processes holds great promise. However, its use for the delivery of nucleic acids has been very scarcely described and the reported procedures are not optimal as they often involve potentially toxic materials and irradiation conditions. This work prepares a simple system made of biocompatible porous silicon nanoparticles (pSiNP) for the safe siRNA photocontrolled delivery and gene silencing in cells upon two-photon excitation. PSiNP are linked to an azobenzene moiety, which possesses a lysine group (pSiNP@ICPES-azo@Lys) to efficiently complex siRNA. Non-linear excitation of the two-photon absorber system (pSiNP) followed by intermolecular energy transfer (FRET) to trans azobenzene moiety, result in the photoisomerization of the azobenzene from trans to cis and in the destabilization of the azobenzene-siRNA complex, thus inducing the delivery of the cargo siRNA to the cytoplasm of cells. Efficient silencing in MCF-7 expressing stable firefly luciferase with siRNAluc against luciferase is observed. Furthermore, siRNA against inhibitory apoptotic protein (IAP) leads to over 70% of MCF-7 cancer cell death. The developed technique using two-photon light allows a unique high spatiotemporally controlled and safe siRNA delivery in cells in few seconds of irradiation.

Aggregation of magnetic nanoparticles functionalized with trans-resveratrol in aqueous solution.

In the framework of a protein-ligand-fishing strategy to identify proteins that bind to trans-resveratrol, a natural phenolic compound with pharmacological benefits, we have developed magnetic nanoparticles covalently linked to trans-resveratrol through three different derivatives and examined their aggregation behavior in aqueous solution. The monodispersed magnetic core (18 nm diameter) with its mesoporous silica shell (93 nm diameter) exhibited a notable superparamagnetic behavior useful for magnetic bioseparation. The hydrodynamic diameter, deduced from dynamic light scattering analysis, of the nanoparticle increased from 100 to 800 nm when the aqueous buffer changed from pH 10.0-3.0. A size polydispersion occurred from pH 7.0-3.0. In parallel, the value of the extinction cross section increased according to a negative power law of the UV wavelength. This was mainly due to light scattering by mesoporous silica, whereas the absorbance cross section remained very low in the 230-400 nm domain. The three types of resveratrol-grafted magnetic nanoparticles exhibited similar scattering properties, but their absorbance spectrum was consistent with the presence of trans-resveratrol. Their functionalization increased their negative zeta potential when pH increased from 3.0 to 10.0. The mesoporous nanoparticles were monodispersed in alkaline conditions, where their anionic surface strongly repulsed each other but aggregated progressively under van der Waals forces and hydrogen bonding when negative zeta potential decreased. The characterized results of nanoparticle behavior in aqueous solution provide critical insight for further study of nanoparticles with proteins in biological environment.

Electronic, steric and catalytic properties of N-heterocyclic carbene rhodium(I) complexes linked to (metallo)porphyrins.

Electronic and steric properties of NHC ligands functionalized with porphyrins were investigated. When porphyrins are used as NHC-wingtips, nickel(II) in the macrocyle significantly improves the catalytic activity of the neighbouring NHC-Rh(I) complex in the conjugate addition of phenylboronic acid to cyclohexen-2-one.

Controlled Anchoring of Iron Oxide Nanoparticles on Polymeric Nanofibers: Easy Access to Core@Shell Organic-Inorganic Nanocomposites for Magneto-Scaffolds.

Composites combining superparamagnetic iron oxide nanoparticles (SPIONs) and polymers are largely present in modern (bio)materials. However, although SPIONs embedded in polymer matrices are classically reported, the mechanical and degradation properties of the polymer scaffold are impacted by the SPIONs. Therefore, the controlled anchoring of SPIONs onto polymer surfaces is still a major challenge. Herein, we propose an efficient strategy for the direct and uniform anchoring of SPIONs on the surface of functionalized-polylactide (PLA) nanofibers via a simple free ligand exchange procedure to design PLA@SPIONs core@shell nanocomposites. The resulting PLA@SPIONs hybrid biomaterials are characterized by electron microscopy (scanning electron microscopy and transmission electron microscopy) and energy-dispersive X-ray spectroscopy analysis to probe the morphology and detect elements present at the organic-inorganic interface, respectively. A monolayer of SPIONs with a complete and homogeneous coverage is observed on the surface of PLA nanofibers. Magnetization experiments show that magnetic properties of the nanoparticles are well preserved after their grafting on the PLA fibers and that the size of the nanoparticles does not change. The absence of cytotoxicity, combined with a high sensitivity of detection in magnetic resonance imaging both in vitro and in vivo, makes these hybrid nanocomposites attractive for the development of magnetic biomaterials for biomedical applications.

Joint Experimental and Computational Investigation of the Flexibility of a Diacetylene-Based Mixed-Linker MOF: Revealing the Existence of Two Low-Temperature Phase Transitions and the Presence of Colossal Positive and Giant Negative Thermal Expansions.

Solvothermal reaction in N,N-dimethylformamide (DMF) between 1,6-bis(1-imidazolyl)-2,4-hexadiyne monohydrate (L1⋅H2 O), isophthalic acid (H2 L2), and Zn(NO3 )2 ⋅6 H2 O gives the diacetylene-based mixed-ligand coordination polymer {[Zn(L1)(L2)](DMF)2 }n (UMON-44) in 38 % yield. Combination of DSC with variable-temperature single-crystal X-ray diffraction revealed the occurrence of two phase transitions spanning the ranges 129-144 K and 158-188 K. Furthermore, the three structurally similar phases of UMON-44 show giant negative and/or colossal positive thermal expansions. These unusual phenomena exist without any change in the contents of the unit cell. DFT calculations using the PBE+D3 dispersion scheme were able to distinguish between these polymorphs by accurately reproducing their salient structural features, although corrections in the size of the unit cell turned out to be necessary for the high-temperature phase to account for its large thermal expansion. In addition, the infrared spectra (vibration frequencies and peak intensities) of these theoretical models were calculated, allowing for univocal identification of the corresponding polymorphs. Last, the limits of our computational method were tested by calculating the phase transition temperatures and their associated enthalpies, and the derived figures compare favorably with the values determined experimentally.

Diacetylenes with Ionic-Liquid-Like Substituents: Associating a Polymerizing Cation with a Polymerizing Anion in a Single Precursor for the Synthesis of N-Doped Carbon Materials.

Imidazolium- and benzimidazolium-substituted diacetylenes with bromide or nitrogen-rich dicyanamide and tricyanomethanide anions were synthesized and used as precursors for the preparation of N-doped carbon materials. On pyrolysis under argon at 800 °C both halide precursors afforded graphite-like structures with nitrogen contents of about 8.5%. When the dicyanamide and tricyanomethanide precursors were thermolyzed at the same temperature, graphite-like structures were obtained that exhibit nitrogen contents in the range 17-20 wt%; thereby, the benefit of associating a polymerizing cation with a polymerizing anion in a single precursor was demonstrated. On pyrolysis at 1100 °C the nitrogen contents of the latter pyrolysates remain high (ca. 6 wt%). Adsorption measurements with krypton at 77 K indicated that the materials are nonporous. The highest electrical conductivity was observed for a pyrolysate with one of the lowest nitrogen contents, which also has the highest degree of graphitization. Thus, the quest for N-rich carbons with high electrical conductivities should include both maximization of the nitrogen content and optimization of the degree of graphitization. Crystallographic investigation of the precursors and spectroscopic characterization of the pyrolysates prepared by heating at 220 °C indicate that construction of the final carbon framework does not involve the intermediate formation of a polydiacetylene.